KR20150009712A - Texture etching solution composition and texture etching method of crystalline silicon wafers - Google Patents
Texture etching solution composition and texture etching method of crystalline silicon wafers Download PDFInfo
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- KR20150009712A KR20150009712A KR20130083980A KR20130083980A KR20150009712A KR 20150009712 A KR20150009712 A KR 20150009712A KR 20130083980 A KR20130083980 A KR 20130083980A KR 20130083980 A KR20130083980 A KR 20130083980A KR 20150009712 A KR20150009712 A KR 20150009712A
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- composition
- compound
- etching
- texture
- silicon wafer
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- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 238000011077 uniformity evaluation Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
Abstract
Description
The present invention relates to a texture etchant composition and a texture etching method for a crystalline silicon wafer capable of minimizing the texture quality deviation and minimizing the reflectance of the surface of a crystalline silicon wafer.
In recent years, solar cells, which are rapidly spreading, are electronic devices that convert solar energy, which is a clean energy source, into direct electricity as a next-generation energy source. P-type silicon semiconductor doped with boron is used as silicon, And a PN junction semiconductor substrate in which an N-type silicon semiconductor layer is formed.
When a light such as sunlight is irradiated to a substrate formed with an electric field by PN junction, electrons (-) and holes (+) in the semiconductor are excited to move freely in the semiconductor, and the electric field generated by the PN junction When it comes in, the electrons (-) lead to the N-type semiconductor and the positive (+) lead to the P-type semiconductor. When an electrode is formed on the surface of a p-type semiconductor and an n-type semiconductor and an electron flows to an external circuit, a current is generated. This principle converts solar energy into electrical energy. Therefore, in order to increase the conversion efficiency of solar energy, the electrical output per unit area of the PN junction semiconductor substrate must be maximized. For this, the reflectance should be lowered and the light absorption amount should be maximized. In consideration of this point, the surface of the silicon wafer for a solar cell constituting the PN junction semiconductor substrate is formed into a fine pyramid structure and the antireflection film is processed. The surface of a silicon wafer textured with a fine pyramid structure lowers the reflectance of incident light having a wide wavelength band to increase the intensity of the absorbed light, thereby enhancing the performance, i.e., efficiency, of the solar cell.
US Pat. No. 4,137,123 discloses a method of texturing a surface of a silicon wafer with a fine pyramid structure by adding 0.5 to 10 wt. % Of silicon is dissolved in a solvent. However, this etchant may cause pyramid formation failure to increase the light reflectance and lower the efficiency.
European Patent No. 0477424 discloses a texture etching method in which oxygen is supplied to a texture etchant in which silicon is dissolved in water of ethylene glycol, potassium hydroxide and a residual amount, that is, an air-bearing process is performed. However, this etching method has a disadvantage in that pyramid formation failure is caused to increase the light reflectance and the efficiency, and also requires installation of a separate air-rating equipment.
Korean Patent No. 0180621 discloses a texture etching solution mixed at a ratio of 0.5-5% of a potassium hydroxide solution, 3-20% by volume of isopropyl alcohol and 75-96.5% by volume of deionized water, and US Patent No. 6,451,218 Discloses a texturing etch solution comprising an alkaline compound, isopropyl alcohol, water soluble alkaline ethylene glycol and water. However, since these etching solutions contain isopropyl alcohol having a low boiling point, it is not economical from the viewpoint of productivity and cost, because it is required to add the additional isopropyl alcohol in the texture process, and the temperature gradient of the etchant is generated due to the added isopropyl alcohol, And the uniformity of the texture may be deteriorated.
In forming a fine pyramid structure on the surface of a crystalline silicon wafer, the present invention controls the difference in the etching rate with respect to the direction of the silicon crystal to prevent over etching by the alkali compound, thereby minimizing the quality deviation of the texture per position, Which is an object of the present invention, to provide a texture etching liquid composition for a crystalline silicon wafer.
Another object of the present invention is to provide a texture etchant composition for a crystalline silicon wafer which does not require the application of a separate etchant component during the etching process and the application of the air-raining process.
Another object of the present invention is to provide a texture etching method using the texture etching liquid composition of the crystalline silicon wafer.
1. A texture etching liquid composition for a crystalline silicon wafer comprising an alkali compound and a compound represented by the following formula:
[Chemical Formula 1]
(Wherein among, R 1, R 2, R 3 and R 4 are independently from each other are hydrogen; or, a hydroxyl group or substituted with amino group or unsubstituted aryl group having a carbon number of 1 to 5 alkyl or C 6 -C 12; R 1, R 2 , R 3 and R 4 are not both hydrogen at the same time).
2. The composition of claim 1 wherein the compound of Formula 1 is selected from the group consisting of N-butyl-N'-isopropyl ethylenediamine, 1,2-bis (2-hydroxyphenyl) ethylenediamine (2-hydroxyethyl) ethylenediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine, N'-tetrakis (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ethylenediamine (N- 2-Hydroxyethyl) ethylenediamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine Wherein the etching solution is at least one selected from the group consisting of silicon oxide, silicon nitride, and silicon nitride.
3. The composition of claim 1, wherein the compound of Formula 1 is contained in an amount of 0.001 to 1% by weight based on 100% by weight of the total etching solution composition.
4. The composition for etching a crystalline silicon wafer according to 1 above, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium.
5. The texture etching liquid composition of crystalline silicon wafer according to 1 above, further comprising a polysaccharide.
6. The composition for etching a crystalline silicon wafer according to 5 above, wherein the polysaccharide is at least one selected from the group consisting of a glucan compound, a fructan compound, a mannan compound, a galactan compound, and a metal salt thereof.
7. The composition of claim 6 wherein the polysaccharide is selected from the group consisting of cellulose, dimethylaminoethylcellulose, diethylaminoethylcellulose, ethylhydroxyethylcellulose, methylhydroxyethylcellulose, 4-aminobenzylcellulose, triethylaminoethylcellulose, Cellulose derivatives such as cellulose, ethylcellulose, methylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin,? -Cyclodextrin,? -Cyclodextrin,? 1 selected from the group consisting of cyclodextrin, hydroxypropyl-beta-cyclodextrin, methyl- beta -cyclodextrin, dextran, sodium dextran sulfate, saponin, glycogen, xylose, lentinan, Crystalline silica, a kind of glucan-based compound, Texture etching liquid composition of the wafer.
8. The texture etching liquid composition for a crystalline silicon wafer according to 1 above, further comprising a monomer polymerized with a monomer substituted with a cyclic compound having 4 to 10 carbon atoms and containing at least one nitrogen atom.
9. The composition of
10. The composition of claim 9 wherein said monomer is selected from the group consisting of N-vinyl pyrrolidone, N-acryloyl morpholine, N-vinylsuccinimide, N-acryloxy succinimide, N-vinyl caprolactam, And at least one selected from the group consisting of N, N-dimethylaniline, N, N-acryloylpyrrolidine, and N-acryloylpyrrolidine.
11. The composition of
12. The composition of
13. The composition of claim 10, wherein the polymer has a Hansen solubility parameter of between 6 and 15.
14. The composition of
15. The texture etch composition of crystalline silicon wafers of claim 1 further comprising a cyclic compound.
16. The composition of claim 15, wherein the cyclic compound has a boiling point of at least 100 < 0 > C.
17. The composition of claim 15, wherein the cyclic compound has a Hansen solubility parameter of between 6 and 15.
18. A method of etching a crystalline silicon wafer with an etchant composition according to any one of claims 1 to 17.
19. The etching method according to 18 above, wherein the etching solution composition is sprayed at a temperature of 50 to 100 DEG C for 30 seconds to 60 minutes.
20. The etching method according to 18 above, wherein the wafer is immersed in the etching solution composition at a temperature of 50 to 100 DEG C for 30 seconds to 60 minutes.
According to the texture etchant composition and the texture etching method of the crystalline silicon wafer of the present invention, the difference in the etching rate with respect to the direction of the silicon crystal is controlled to prevent the overetching by the alkali compound, To maximize the absorption of sunlight by improving the uniformity of the texture.
There is no need to add a separate etching solution component in the texture process and there is no need to introduce air rating equipment, which can improve quality and productivity, and is economical in terms of process cost.
1 is an optical microscope photograph showing a texture of a single crystal silicon wafer etched using the etching solution composition for a texture of the crystalline silicon wafer of Example 1. Fig.
2 is an optical microscope photograph showing the surface of a single crystal silicon wafer textured with an etching solution composition for a texture of a crystalline silicon wafer of Comparative Example 1. Fig.
3 is an optical microscope photograph showing the surface of a single crystal silicon wafer textured with the etching solution composition for a texture of the crystalline silicon wafer of Comparative Example 2. Fig.
The present invention includes an alkaline compound and a compound of the formula (1) to control the difference in the etching rate with respect to the direction of the silicon crystal in forming a fine pyramid structure on the surface of the crystalline silicon wafer to prevent over etching by the alkali compound To a texture etchant composition and a texture etching method for a crystalline silicon wafer which improves light efficiency by minimizing the quality deviation of texture by position.
Hereinafter, the present invention will be described in detail.
The texture etchant composition of the crystalline silicon wafer of the present invention is characterized by containing a compound represented by the following formula (1).
[Chemical Formula 1]
R 1 , R 2 , R 3 and R 4 independently of one another are hydrogen; Or an alkyl having 1 to 5 carbon atoms or an aryl having 6 to 12 carbon atoms, which is unsubstituted or substituted with a hydroxyl group or an amino group; R 1 , R 2 , R 3 and R 4 are not all simultaneously hydrogen.
The compound of formula (1) according to the present invention can control the difference in the etching rate with respect to the direction of the silicon crystal to prevent the over etching by the alkali compound, thereby minimizing the quality deviation of the texture.
The compound of formula (1) is not particularly limited, and examples thereof include N-butyl-N'-isopropyl ethylenediamine, 1,2-bis (2-hydroxyphenyl) ethylenediamine (2-hydroxyethyl) ethylenediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine, N'-tetrakis (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ethylenediamine (N- 2-hydroxyethyl) ethylenediamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine . These may be used alone or in combination of two or more.
The compound of the formula (1) may be contained in an amount of 0.001 to 1% by weight, preferably 0.001 to 0.5% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. The effect of controlling the etching rate difference with respect to the crystal direction of silicon without the etching and unetching is maximized when the content falls within the above range.
The etching solution composition according to the present invention further comprises an alkaline compound.
The alkali compound can be used without limitation as long as it is an alkaline compound commonly used in the art as a component for etching the surface of a crystalline silicon wafer. Examples of the alkali compound that can be used include potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium. Of these, potassium hydroxide and sodium hydroxide are preferable. These may be used alone or in combination of two or more.
The alkali compound is preferably contained in an amount of 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, the surface of the silicon wafer can be etched.
Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a polysaccharide.
A polysaccharide is a saccharide in which two or more monosaccharides are linked by a glycosidic bond to form a large molecule. By preventing over etching and accelerated etching by an alkaline compound, a uniform fine pyramid is formed, and a hydrogen bubble generated by etching It is a component that prevents the bubble stick phenomenon by dropping rapidly from the silicon wafer surface.
Examples of the polysaccharide include a glucan compound, a fructan compound, a mannan compound, a galactan compound, or a metal salt thereof. Among them, a glucan compound and its metal salt (for example, , Alkali metal salts) are preferable. These may be used alone or in combination of two or more.
Examples of the glucan compound include cellulose, dimethylaminoethylcellulose, diethylaminoethylcellulose, ethylhydroxyethylcellulose, methylhydroxyethylcellulose, 4-aminobenzylcellulose, triethylaminoethylcellulose, cyanoethylcellulose, ethylcellulose, But are not limited to, cellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin,? -Cyclodextrin,? -Cyclodextrin, Cyclodextrin, methyl- beta -cyclodextrin, dextran, sodium dextran sulfate, saponin, glycogen, zymo acid, lentinan, sijofinan or metal salts thereof.
The polysaccharide may have an average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 200,000.
The polysaccharide may be contained in an amount of 10 -9 to 0.5% by weight, preferably 10 -6 to 0.1% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, etching and etching acceleration can be effectively prevented. When the content is more than 0.5% by weight, the etching rate by the alkali compound is rapidly lowered and it is difficult to form the desired fine pyramid.
Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a polymer in which a monomer substituted with a cyclic compound having 4 to 10 carbon atoms containing at least one nitrogen atom is polymerized.
By controlling the difference in the etching rate with respect to the direction of the silicon crystal, the polymer prevents the over etching by the alkaline compound, thereby minimizing the quality deviation of the texture. By rapidly reducing the amount of hydrogen bubbles generated by etching, the bubble stick phenomenon Is suppressed.
The polymer according to the present invention is formed by polymerizing monomers substituted with a cyclic compound having 4 to 10 carbon atoms and having at least one nitrogen heteroatom, and the monomer may contain oxygen or sulfur atoms alone or in combination with at least one And may further include the ring structure. Specific examples of such monomers include N-vinylpyrrolidone, N-acryloylmorpholine, N-vinylsuccinimide, N-acryloxysuccinimide, N-vinylcaprolactam, N-vinylcarbazole, N-acryloylpyrrolidine, and the like.
The polymer according to the present invention has a weight average molecular weight of 1,000 to 1,000,000, which is preferable because it can lower the reflectance by increasing the angle of the base of the pyramid, and can form a uniform pyramid on the entire surface of the single crystal silicon wafer.
The polymer according to the present invention has a boiling point of 100 ° C or higher, which is preferable in view of reducing the amount of use, and more preferably 150 to 400 ° C. At the same time, the polymer according to the present invention preferably has a solubility parameter (Hansen solubility parameter (HSP),? P) of 6 to 15 in terms of compatibility with other components contained in the etchant composition.
The content of the polymer according to the present invention may be in the range of 10 -12 to 1% by weight based on the total weight of the etchant composition. When the content is within the above range, the effect of controlling the etching rate difference with respect to the crystal direction of silicon is maximized.
The polymer according to the present invention may be mixed with a water-soluble polar solvent.
The type of the water-soluble polar solvent is not particularly limited as long as it is compatible with other components contained in the texture etching solution composition of the crystalline silicon wafer and with water, and both quantum and aprotic polar solvents can be used.
Examples of the protonic polar solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether , Diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; And alcoholic compounds such as propanol, butanol, isopropanol, tetrahydroperfuryl alcohol, ethylene glycol and propylene glycol. Examples of the aprotic polar solvent include amides such as N-methylformamide and N, N-dimethylformamide Based compound; Sulfoxide compounds such as dimethyl sulfoxide and sulfolane; And phosphate-based compounds such as triethyl phosphate and tributyl phosphate. These may be used alone or in combination of two or more.
Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a cyclic compound.
The cyclic compound is a cyclic hydrocarbon having 4-10 carbon atoms; And a heterocyclic hydrocarbon having 4 to 10 carbon atoms and containing at least one hetero atom of N, O or S. The wettability of the surface of the crystalline silicon wafer is improved, Thereby minimizing the quality deviation of the texture, and at the same time, rapidly reducing the amount of hydrogen bubbles generated by etching, thereby preventing occurrence of bubble stick phenomenon. In addition, since it has a high boiling point, it can be used in a small amount as compared with isopropyl alcohol which is conventionally used, and the number of treatments for the same amount can also be increased.
The cyclic compound preferably has a boiling point of 100 占 폚 or higher, more preferably 150 to 400 占 폚. At the same time, the cyclic compound preferably has a solubility parameter (Hansen solubility parameter (HSP),? P) of 6 to 15 in terms of compatibility with other components contained in the etchant composition.
The type of the cyclic compound is not particularly limited so long as it satisfies the solubility parameter of the boiling point and Hansen. Examples of the cyclic compound include piperazine, morpholine, pyridine, piperidine, piperidone, pyrrolidine, Imidazolidinone, furan, aniline, toluidine, amine, lactone, carbonate, and carbazole compounds. Specific examples include piperazine, N-methylpiperazine, N-ethylpiperazine, N-vinylpiperazine, N-vinylmethylpiperazine, N-vinylethylpiperazine, N-vinyl- N-acryloylpiperazine, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpiperazine; Methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-vinylmorpholine, N-vinylmethylmorpholine, N-vinylethylmorpholine, N-acryloylmorpholine, N N- (2-hydroxyethyl) morpholine, N- (2-hydroxyethyl) morpholine, N- Morpholine, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide; Methyl pyridine; N-methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine; N-vinylpiperidone, N-vinylmethylpiperidone, N-vinylethylpiperidone, N-acryloylpiperidone, N-methyl-4-piperidone, N-vinyl-2-piperidone; N-methylpyrrolidine; N-vinylpyrrolidone, N-vinylmethylpyrrolidone, N-vinylethyl-2-pyrrolidone, N-acryloylpyrrolidone, N-methylpyrrolidone, Butyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-butyl- Pyrrolidone, N-benzyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N- - (2-methoxyethyl) -2-pyrrolidone, N- (2-methoxypropyl) -2-pyrrolidone, N- (2-ethoxyethyl) -2-pyrrolidone; N-methylimidazolidinone, dimethylimidazolidinone, N- (2-hydroxyethyl) -2-imidazolidinone; Tetrahydrofuran, tetrahydro-2-furan methanol; N, N-dimethylaniline, N, N-bis (2-hydroxyethyl) aniline, N-ethyl- 2-hydroxyethyl) aniline; N, N-diethyl-o-toluidine, N-ethyl-N- (2-hydroxyethyl) -m-toluidine; Dimethylbenzylamine; ? -butyrolactone; Ethylene carbonate, propylene carbonate; N-vinylcarbazole, N-acryloylcarbazole, etc. These may be used alone or in admixture of two or more.
The cyclic compound is preferably contained in an amount of 0.1 to 50% by weight, more preferably 1 to 10% by weight based on 100% by weight of the total amount of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, the wettability of the surface of the silicon wafer is effectively improved, thereby minimizing the texture quality deviation, thereby improving the uniformity.
The cyclic compound may be mixed with a water-soluble polar solvent.
As the water-soluble polar solvent, the same solvent as that of the above-mentioned polymer can be used. The water-soluble polar solvent may be contained in an amount of 0.1 to 30% by weight based on 100% by weight of the total amount of the cyclic compound.
Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may comprise a fatty acid or a metal salt thereof; And at least one additive selected from the group consisting of a polyoxyethylene (POE) compound, a polyoxypropylene (POP) compound, and a copolymer thereof, which are surfactants.
Fatty acids and their metal salts are used in combination with polysaccharides to prevent over-etching by alkaline compounds to form uniform fine pyramids and at the same time to quickly drop hydrogen bubbles generated by etching from the silicon wafer surface to prevent bubble sticking Lt; / RTI >
The fatty acid is a carboxylic acid of a hydrocarbon chain containing a carboxy group and specifically includes acetic acid, propionic acid, butyric acid, valeric acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, But are not limited to, stearic acid, arachidic acid, behenic acid, lignoceric acid, cetric acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid,? -Linolenic acid,? -Linolenic acid, dihomo- Oleic acid, elaidic acid, erucic acid, nerbonic acid, and the like. The metal salt of the fatty acid may be an ester reaction product of a fatty acid and a metal salt such as NaOH or KOH. These may be used alone or in combination of two or more.
The fatty acid and its metal salt may be contained in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, etching can be effectively prevented.
And Si 100 direction by controlling the activity of-a polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof is a hydroxy ion [OH] of the texture etching solution composition as a surface active agent having a hydroxy group Not only the difference in the etching rate with respect to the Si 111 direction is reduced but also the wettability of the surface of the crystalline silicon wafer is improved to rapidly drop the hydrogen bubble generated by the etching to prevent the occurrence of the bubble stick phenomenon.
Examples of the polyoxyethylene (POE) surfactant include polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, polyoxyethylene neopentyl ether, polyethylene glycol mono (tristyrylphenyl) ether, polyoxyethylene Polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene bisphenol-A, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Ether, polyoxyethylene glycerin ether, polyoxyethylene nonylphenyl ether, polyoxyethylene benzyl ether, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene phenol ether, polyoxyethylene having 6 to 30 carbon atoms in the alkyl group Ethylene alkyl cyclohexyl ether, polyoxyethylene beta -naphthol ether, polyoxyethylene Ethylene castor ether (polyoxyethylene castor ether), polyoxyethylene hydrogenated castor ether (polyoxyethylene hydrogenated castor ether); Polyoxyethylene lauryl ester, polyoxyethylene stearyl ester, polyoxyethylene oleyl ester; Polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylenetraelamine, and the like. As the polyoxypropylene (POP) surfactant, polypropylene glycol can be mentioned. As a copolymer of a polyoxyethylene (POE) compound and a polyoxypropylene (POP) based compound, a polyoxyethylene-polyoxypropylene copolymer, a polyoxyethylene-polyoxypropylene decaneyl ether copolymer, a polyoxyethylene Polyoxyethylene-polyoxypropylene dodecanyl ether copolymer, polyoxyethylene-polyoxypropylene tetradecanyl ether copolymer, polyoxyethylene-polyoxypropylene 2-ethylhexyl ether copolymer Polyoxyethylene-polyoxypropylene lauryl ether copolymer, polyoxyethylene-polyoxypropylene stearyl ether copolymer, glycerin addition type polyoxyethylene-polyoxypropylene copolymer, ethylenediamine addition type polyoxyethylene-polyoxypropylene Copolymers and the like. These may be used alone or in combination of two or more.
The polyoxyethylene (POE) compound, the polyoxypropylene (POP) compound and the surfactant which is a copolymer thereof may be contained in an amount of 10 -9 to 10% by weight based on the total weight of the texture etching liquid composition of the crystalline silicon wafer, Is preferably 10 -6 to 1% by weight, more preferably 0.00001 to 0.1% by weight. When the content falls within the above range, it is possible to reduce a variation in the texture quality of the surface of the crystalline silicon wafer at each texture position.
The texture etchant composition of the crystalline silicon wafer according to the present invention may appropriately employ the above-mentioned components according to specific needs, and then add water to adjust the overall composition, so that the remaining amount of the entire composition is occupied by water. Preferably, the components are adjusted to have the aforementioned content ranges.
The kind of water is not particularly limited, but it is preferably deionized distilled water. More preferably, it is deionized distilled water for semiconductor processing and has a resistivity value of 18 M OMEGA. / Cm or more.
The texture etchant composition of the crystalline silicon wafer of the present invention, which comprises the above-described components, particularly includes the compound of the formula (1), thereby controlling the difference in the etching rate with respect to the direction of the silicon crystal, Thus, it is possible to maximize the amount of sunlight absorption by minimizing the quality deviation of the texture of the crystalline silicon wafer surface by position, that is, by improving the uniformity of the texture. In addition, there is no need to add a separate etching solution component in the texture etching process and there is no need to introduce an air-rating equipment, which is advantageous in terms of productivity and cost.
The texture etchant composition of the crystalline silicon wafer of the present invention can be applied to a general etching process, for example, a dip process, a spray process, and a sheet-process etching process.
The present invention provides a method of etching a crystalline silicon wafer using the texture etchant composition of the crystalline silicon wafer.
The method of texturing a crystalline silicon wafer includes the steps of depositing a crystalline silicon wafer on the texture etchant composition of the crystalline silicon wafer of the present invention or by spraying a textured etchant composition of the crystalline silicon wafer of the present invention onto a crystalline silicon wafer Step, or both of the above steps.
The number of times of deposition and spraying is not particularly limited, and the order of deposition and spraying is not limited.
The step of depositing, spraying or depositing and spraying can be carried out at a temperature of 50 to 100 캜 for 30 seconds to 60 minutes.
The texture etching method of the crystalline silicon wafer of the present invention as described above is not only economical in terms of initial production and processing cost but also requires no separate airrating equipment for supplying oxygen, Structure.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
Example 1-11 and Comparative Example 1-8
A residual amount of water was added to the components and composition ratios (% by weight) described in Table 1 below to prepare an etching liquid composition for a texture of a crystalline silicon wafer.
AEP
0.2
GBL
0.2
BPED: N-butyl-N'-isopropylethylenediamine
BHPED: 1,2-bis (2-hydroxyphenyl) ethylenediamine
BHEED: N, N'-bis (2-hydroxyethyl) ethylenediamine
THEED: N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine
HEED: N- (2-hydroxyethyl) ethylenediamine
THPED: N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine
EDTA: Ethylenediaminetetraacetic acid (EDTA)
DTPA: Diethylene triaminepentaacetic acid (DTPA)
CDTA: trans-1,2-cyclohexanediaminetetraacetic acid (trans-1,2-cyclohexanediaminetetraacetic acid)
ED: Ethylenediamine
CMCNa: Carboxyl methyl cellulose sodium salt
NMP: N-methylpyrrolidone AEP: Aminoethylpiperazine,
GBL:? -Butyrolactone
PNAM: poly (N-acryloylmorpholine), PNVP: poly (N-vinylpyrrolidone)
Experimental Example
Single crystal silicon wafers were immersed and etched in the etching solution compositions for texturing of the crystalline silicon wafers of Examples 1 to 10 and Comparative Examples 1 to 8, respectively. At this time, the texture condition was a temperature of 80 ° C and a time of 20 minutes.
One. Texture Uniformity evaluation
(Example 1), Fig. 2 (Comparative Example 1), and Fig. 3 (Comparative Example 2). The results are shown in Table 2 and Fig. Respectively.
◎: Formation of wafer front pyramid
?: Some of the wafers were not pyramid-formed (less than 5% of the pyramid structure was not formed)
DELTA: Some of the wafers were not pyramid-formed (degree of pyramidal structure unformed to 5 to 50%)
Х: Wafer pyramid not formed (pyramid not formed 90% or more)
2. Texture Reflectance evaluation
The texture reflectance was measured by measuring the average reflectance when light having a wavelength band of 400 to 800 nm was irradiated using ultraviolet rays, and the results are shown in Table 2.
Referring to Table 2 and FIG. 1, it can be seen that the etchant composition for texturing silicon wafers of Examples 1 to 11 has a very good degree of forming a pyramid on the entire surface of a single crystal silicon wafer. Because of this texture uniformity and pyramid shape, it can be seen that the silicon wafer textures formed in embodiments exhibit low reflectance values of about 10-12%.
It was confirmed that pyramid formation at high magnification was confirmed by 3D optical microscope or SEM analysis. As a result, high density pyramid was formed.
However, in the etchant composition for texturing of wafers of Comparative Examples 1 and 5 to 8, a pyramid is formed on the entire surface of the wafer as in Fig. 2 (Comparative Example 1), but the pyramid is crushed in many portions, And the degree of pyramid formation was poor.
In Comparative Examples 2 to 4, it was confirmed that pyramids were not formed in 90% or more of the wafers as in Fig. 3 (Comparative Example 2). Also, the etching was excessive and the surface of the silicon wafer showed a very bright surface.
Claims (20)
[Chemical Formula 1]
(Wherein among, R 1, R 2, R 3 and R 4 are independently from each other are hydrogen; or, a hydroxyl group or substituted with amino group or unsubstituted aryl group having a carbon number of 1 to 5 alkyl or C 6 -C 12; R 1, R 2 , R 3 and R 4 are not both hydrogen at the same time).
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